Condensation products of bis-aminotriazines



Patented Sept. 22, 1953 UNITED STATES PATENT OFFICE CONDENSATIONPRODUCTS OF BIS-AMINOTRIAZINES Peter L. de Bonneville, Philadelphia, andVincent Carr Mennier, Flourtown, Pa., assignors to Rohm & Haas Company,Philadelphia, Pa., a corporation of Delaware No Drawing. ApplicationMarch 12, 1952, Serial No. 276,233

tone. In the preparation of the bis-(aminotriazines) useful for thepractice of this invention the primary amine used in reaction (1) shouldbe one having a normal or secondary but not a ter- NHI R tiary alkylgroup such as methylamine, ethylamine, propylamine, isopropylamine,normal bu- N tylamine, secondary butylamine, isobutylamine, I orz-ethylhexylamine. The carbonyl compound should be one in which R1 ishydrogen or methyl in which R is an alkyl group of from one to eightcarbon atoms and which contains a hydrogen atom on the carbon atomadjacent the nitrogen atom, R1 is a hydrogen or a methyl group, and R2is an alkyl group of one to eight carbon atoms. We have found thatbis-(aminotriazines) or this structure react readily ,with formaldehydeor with formaldehyde and an alcohol to give condensates having a varietyof industrial uses. In many ways these new condensates are superior tothe aminotriazine resins now commercially available.

In copending applications Serial Nos. 218,231 and 276,232, filed on evendate herewith, it is shown that bis-(aminotriazines) of the aboveiormula can be made by the following series of reactions:

R Bi 1) mm, d=0 HCN RN--'.JJCN 11,0

place between a primary amine and a cyanohydrin iormed from I-ICN and analdehyde or keand R: is an alkyl group of one to eight carbon atoms.Representative carbonyl compounds are acetaldehyde, propionaldehyde,acetone, methyl ethyl ketone, and nonylaldehyde.

Reaction (2) is carried out on the alkaline side in an inert solventsuch as benzene at room temperature or slightly above room temperatureup to about 50 C. The reaction is exothermic and should be carried outin reactors equipped with cooling means.

Reaction (3) is carried out in an inert solvent such as a lower alcoholand in the presence of a small amount of alkaline catalyst The reactionis carried out at the reflux temperature and is usually accompanied byan cxotherm. The bis-(aminotriazine) precipitates from the reactionmedium as it is formed and is readily freed from excess dicyanodiamineby a hot water wash.

From the above formulae it can be observed that the bis-(aminotriazine)obtained by this series of reactions is with respect to one of thetriazine rings a substituted melamine and with respect to the other asubstituted guanamine. We have caused them to react with formaldehydeand with formaldehyde and alcohol to give products of various degrees ofcondensation and have found that these condensation products havevaluable industrial usage. The initial condensation product or A"-stagecondensate is a methylol compound that may, among other things, be usedto stabilize rayon against shrinking without deleterious effects uponabrasion-resistance. The moderately condensed "B-stage product was founduseful in stabilizing wool against shrinkage and as an adhesive. Themore highly condensed B-stage products are even better stabilizers 01wool against shrinkage and are excellent wet-strength paper resins. Themethylated resins formed by the reaction of the bis-(aminotriazine) withformaldehyde and methyl alcohol are water-soluble products that may beused to stiflen nylon, and the butylated resins are soluble in organicsolvents and make excellent coating compositions.

In the preparation of these condensation products from six to ten mols0! formaldehyde may EXAMPLE A A. Preparation 01 CHI Over a period twohours 132.2 parts of gaseous monomethylamine was added to 340.4 parts ofacetone cyanohydrin. During the addition the temperature was kept in therange of C. to +10 C. The reaction mixture was then stripped at roomtemperature and used in Part B without further purification.

B. Preparation 01' The crude aminonitrile as prepared in part A wasmixed at 10 C. with 352 parts 0! benzene, 276.8 parts of anhydrouspotassium carbonate, and 128 parts of water. There was then added at -25C. and over a period 01 65 minutes 246 parts of cyanogen chloride.Stirring was continued for one-half hour at room temperature and thereaction mixture allowed to stand overnight. It was then heated to 50C., cooled, the aqueous layer separated, and the benzene layer filtered,dried over anhydrous magnesium sulfate and distilled. There was obtained213.5 parts of. a light brown oil boiling at 8990 C. at 2 mm.

C. Preparation of N NH:

EXAMPLEB A. Preparation of o.m-N- CN Over a period of 15 minutes and ata temperature o1 25"-40 C. 127.4 parts or acetone cyanohydrin was addedto 120.5 parts of n-butylamine. Stirring was continued for 75 minutes atroom temperature and then for 30 minutes at 50 C. The reaction mixturewas cooled to room temperature and benzene added. Seventeen parts oiwater was separated. The benzene layer was distilled and yielded 182parts of aminonitrile as a pale yellow liquid boiling at 8648 C. at 28mm.

B. Preparation of CH|N CN To a stirred solution or 44 parts of benzeneand 30.8 parts of cyanogen chloride there was added a solution 01 71.3parts of aminonitrile prepared as in part A in 88 parts of benzene. Theaddition was made at 20-40 C. over a period or 30 minutes. A solution of34.5 parts of anhydrous potassium carbonate in 35 parts or water wasthen added in 15 minutes at 28-35 C. The reaction mixture was stirredfor two hours at room temperature and for 15 minutes at 50 C. It wasthen cooled, filtered, and the benzene layer distilled. Forty-five partsof cyanoaminonitrile was obtained as a pale yellow liquid boiling at 96C. at 1 mm.

C. Preparation of To a stirred mixture of 44 parts of isopropanol, 23.2parts 01 cyanoaminonitrile as prepared in part B, and 25.9 parts 01dicyanodiamide there was added at reflux C.) a solution of 4.6 parts of85% potassium hydroxide in 56 parts 01' isopropanol. The addition wasmade over a period 01' 15 minutes by which time all ingredients were insolution. Heating at reflux was continued and after 30 minutes somesolid precipitated. The refluxing was continued for an additional sixhours and the reaction mixture was then cooled, filtered and washed withhot water. Twenty-two parts of bis-triazine, a white solid melting at271-272 C., was obtained.

EXAMPLE C A. Preparation of To a mixture of 166 parts of3,5,5-trimethylhexaldehyde cyanohydrin and 40 parts of benzene there wasadded 32.5 parts of methylamine. The addition was made at 15-20 C. overa period of one and one-half hours. The addition of more benzene causedthe separation or 16 parts of water which was removed. The benzene layerwas then dried over anhydrous sodium suli'ate and stripped at 100 C. at16 mm. There was obtained 168.8 parts of the aminonitrile.

B. Preparation of a CHr-NCN N tHn A solution or 98.6 parts or the aboveaminonitrile in 40 parts of benzene was added at 20 C. and over a 30minute period to a solution of 33.9 parts of cyanogen chloride in 40parts of benzene. To this mixture was then added at 10-15 C. and over aminute period a solution of 34.5 parts of potassium carbonate in 40parts of water. The reaction mixture was stirred at room temperature forone hour, filtered, and the water layer separated. The benzene layer wasdistilled to yield 90.5 parts of the cyanoaminonitrile boiling at133-140 C. at 1.5 mm.

C. Preparation of N N-C CHr-N-JC sH1'| N=C To a mixture of 38.6 parts ofthe cyanoaminonitrile of part B, 40 parts of isopropanol, and 37 partsof dicyanodiamide there was added quite rapidly at 85 C. a solution of6.6 parts of potassium hydroxide, reagent grade. in 80 parts ofisopropanol. The mixture was refluxed for 22 hours, filtered at roomtemperature, and the residue washed with hot water (65 0.). 0nair-drying, there was obtained 40 parts of solid product melting at256-258 C.

Analogous bis-(aminotriazines) within the class above-defined can bemade following these procedures and selecting other primary amines andketones. The bis-(aminotriazines) are con verted to the products of thisinvention by procedures illustrated by the following examples:

EXAMPLE 1 Preparation of A-stage condensation products Into a flaskequipped with thermometer, reflux condenser, and mechanical agitatorwere charged 163.2 parts of 36.7% aqueous formaldehyde (2 mols) and 625parts of water. The pH of the solution was adjusted to 8.1 with 10%aqueous soda ash solution. To the formaldehyde solution was added 7275parts (0.25 mol) of the bis-(aminotriazine) of Example A. The mixturewas heated to 80 C. and after one hour a clear solution was obtained.The product was cooled with an ice-bath and filtered with Super Ce]. Ithad the following physical properties:

Solids 13.1% Viscosity centipoises pH 8.2

A rayon fabric was padded through a 4.3% aqueous solution of thecondensate adjusted with phosphoric acid to pH 4 and squeezed to a wetpick-up of about 90%. The treated fabric was cured for ten minutes at300 F. Shrinkage tests showed 3.3% shrinkage as against 8.0% for theuntreated fabric.

EXAMPLE 2 Preparation of moderately condensed "B-stage condensationproducts A sample of condensate prepared as described in Example 1 wasstripped in vacuo from 13.1% solids concentration to 54.7%. At the endof the stripping the viscosity was 1.4 poises and the pH 7.9. Thecondensate was heated at 80 C. for

an hour after which time the viscosity rose to 2.7 poises. The resin wascooled to room temperature.

The reaction product was applied to wood laminae which were thenassembled into a plywood and hot-bonded for four minutes at 250 F. Bothcatalyzed (7% NHiSCN) and uncatalyzed formulations gave boil-resistantbonds in the plywood. The catalyzed formulations when used incold-bonding (24 hours in cold clamps plus six days conditioning at 75F.) also gave boilresistant bonds.

A wool flannel, free of grease and spinning oils, was padded through asolution containing 3% of the resin, a small amount or a syntheticnon-ionic wetting agent, and 1% of phosphoric acid. After passingthrough squeeze rolls the padding was repeated with the result that theimpregnated flannel had a wet pick-up of 75%. It was dried in an oven at240 F. for ten minutes. No shrinkage was measurable even after fivewashings.

EXAMPLE 3 Preparation of highly condensed B-stage condensation productsA sample of condensate prepared as described in Example 2 was dilutedwith distilled water to 20% solids concentration. Suflicient 37%hydrochloric acid was added to lower the pH to 2.0. This required aboutone mol of hydrochloric acid per mol of bis-(aminotriazine) contained inthe sample. The treated sample was aged for three days at 27-30 C. atthe end of which time its viscosity had increased from about 20 to 125centipoises. The solution was stabilized by dilution with distilledwater to 10% solids concentration.

Bleached sulfite pulp was beaten at 2% to a Canadian ireeness value of600. It was then diluted to one percent and to a 2 kg. sample in 2.Valley disintegrator there was stirred in suflicient 10% solution of theresin to provide 0.4 g. of resin solids. The pH of the pulp was adjustedto 4 by the addition of hydrochloric acid. It was then diluted toone-quarter percent and a 1300 ml. sample was run into a sheet mold anda sheet 8 1: 8 /2" formed. The sheet was pressed for two minutes at p.s. i., dried for ten minutes at 200 F., and finally aged at 75 F. and50% relative humidity. At intervals it was tested for wet strength using4" x 1" strips soaked in water for one hour. After 28 days the treatedpaper had a wet tensile strength of 4.1 lbs/in. and a dry tensilestrength of 14.6 lbs./in. as compared with a wet tensile of 0.5 lb./in.and a dry tensile oi 10 lbs./in. for the untreated paper.

EXAMPLE 4 Preparation of "A"-stuge alcohol-modified condensationproducts Into a three-necked flask equipped with a thermometer, refluxcondenser, and mechanical agitator were charged 192 parts (6.0 mols) ofmethanol and a mixture of 48.3 parts oi flake (91%) paraiormaldehyde and11.3 parts or 36.1% aqueous formaldehyde (totalling 1.60 mols oi HCHO).The pH was raised to 8.4-8.6 (cresol red) with 25% sodium hydroxidesolution. The mixture was heated to 70 C. and after one-half hour aclear solution was obtained. Next, 58.2 parts (0.2 moi) of theditriazine or Example A was added and the resultant mixture was heated 7at reflux (73 C.) tor one-halt hour (pH 8.4-8.8- cresol red). The pH waslowered to and held at 3.8-4.0 (bromocresol green) by repeated additionsof 90% formic acid. Alter heating for one hour (73 C.) a clear solutionwas obtained. The product was cooled with an ice-bath and the pH wasadjusted to 7.0-7.2 (bromothymol blue) with 40% sodium hydroxidesolution. The product was filtered with Super Cel. It had the followingphysical properties:

Solids 35.3%

Viscosity (25 C.) 0.5 poise Water tolerance (25 C.) 10 cc./10 g. resinpH (bromothymol blue) 7.0-7.2

A sample of the product thus obtained was diluted to 12.5% resin contentwith 10% phosphoric acid. Scoured nylon tafleta was padded through,given a light squeeze, dried at room temperature, and cured at 300 F.for ten minutes. The resulting fabric was leathery and very stiff butpossessed a full hand. The finish was resistant to washing.

EXAMPLE 5 Preparation of "B"-stage alcohol-modified condensation productfrom the bis-(aminotriazine) of Example A Into a three-necked flaskequipped with reflux condenser, mechanical agitator, thermometer, andwater separator were charged 72.75 parts (0.25 mol) of the ditriazine ofExample A, 124.0 parts (1.5 mols oi. HCHO) of a solution of formaldehydein n-butyl alcohol prepared from 49.6 parts of paraformaldehdye (91%)and 74.4 parts of n-butyl alcohol, 124.0 additional parts 01' n-butylalcohol and 29.0 parts of xylol. The pH of the reaction mixture was7.2-7.4 (bromothymol blue). The mixture was heated to reflux temperature(110 C.) and held at that temperature for 30 minutes. At this point thepH was lowered to 4.6-4.8 (bromocresol green) with 50% aqueous formicacid. Refluxing was resumed. The resin was refluxed under conditions ofcontinuous removal of the aqueous phase forming in the separator. Afterone hour the resin was clear. After three and one-half hours a total or21.0 parts of aqueous phase had separated. The resin was stripped to acalculated 70% solids. The batch temperature rose to 132 C. At thisstage the resin was swept with 50.0 parts oi. butanol. The resin wasthen diluted with butanol, cooled, and filtered with filter aid. It hadthe following physical properties:

Solids 61.4% Viscosity 2.8 poises Mineral thinner tolerance InfiniteIsooctane tolerance Infinite Acid number 2.5 Color (P. and V. scale) 2.

The product thus obtained was incorporated in a baking enamel having thefollowing formulation:

50% titanium dioxide 50% binder 70% Commercial alkyd resin from phthalicacid,

glycerol, and cocoanut oil acids 30% nitrogen resin or this examplereduced to proper viscosity with xylol.

This enamel cured rapidly and gave a coating film that possessedexcellent adhesion, gloss, and alkalland soap-resistance.

8 EXAMPLEB Preparation of "B-staae alcohol-modified condensation productfrom. the bis-(ammoniazine) of Example B Into a three-necked flaskequipped with reflux condenser, mechanical agitator, thermometer, andwater separator were charged 83.3 parts (0.25 mol) of the ditriazine ofExample 13, 124.0 parts (1.50 mols oi! HCHO) of a solution oftormaldehyde in n-butyl alcohol prepared from 49.6 parts ofparatormaldehyde (91%) and 74.4 parts or n-butyl alcohol, 32.0additional parts of nbutyl alcohol, and 33.3 parts of xylol. The pH ofthe reaction mixture was 8.0-8.1 (thymol blue). The mixture was heatedto reflux temperature (115 C.) and held for 15 minutes during which timethe mixture became clear. At this point the pH was lowered to 4.6-4.8(bromocresol green) with 50% aqueous formic acid. Refluxing was resumedunder conditions of contin uous removal of aqueous phase forming in theseparator. After three hours a total or 225 parts of aqueous phase hadseparated. The resin was "swept with 83.0 parts of n-butyl alcohol andthen stripped to a calculated 75% solids.. The batch temperature rose to131 C. The resin was then diluted with xylol, cooled, and filtered withSuper Cel. It had the following physical properties:

Solids 60.7% Viscosity (25 C.) 2.7 poises Mineral thinner toleranceInfinite Isooctane tolerance Infinite Acid number 0.64 Color (P. and V.scale) 1 This resin also gave an excellent coating film whenincorporated in a baking enamel formulated as in Example 5.

EXAMPLE 7 Preparation of B-stage Alcohol-modified Cortdensation Productfrom the Bis-(aminotriazine) of Example C Into a three-necked flaskequipped with reflux condenser, mechanical agitator, thermometer, andwater separator were charged 37.5 parts (0.1 mol) of the ditriazine ofExample C, 49.6 parts (0.6 mol of HCHO) of a solution of formaldehyde inn-butyl alcohol prepared from 19.85 parts of paraformaldehyde (91%) and29.75 parts of n-butyl alcohol, 13.0 addiitona1 parts of n-butylalcohol, and 14.6 parts of xylol. The pH of the reaction mixture was7.2-7.4 (bromothymol blue). The mixture was heated to reflux temperature(115 C.) and held for 15 minutes at this temperature. During this timethe resin became clear. The pH was lowered to 4.6-4.8 (bromocresolgreen) with 50% aqueous formic acid. The resin was then refluxed withcontinuous removal of the aqueous phase forming in the separator. Afterone and one-half hours, a total of 6.5 parts of aqueous phase hadseparated. At this point the resin was swept with 37.0 parts of n-butylalcohol and then stripped to a calculated 75% solids. The batchtemperature rose to 138 C. The resin was then diluted with xylol,cooled, and filtered with Super Cel. It had the following physicalproperties:

Solids 53.7% (acid catalyzed) Viscosity 2.4 poises Mineral thinnertolerance Infinite Isooctane tolerance ml./l0 g. Acid number 2.4

Color (P. and V. scale) 3+ This resin also gives excellent coating iilmswhen incorporated in baking enamels.

In place of the butanol used in Examples 5, 6, and 7 other monohydricalcohols such as propanol, octyl alcohol, and benzyl alcohol may be usedto give condensation products that are soluble in organic solvents. Suchcondensation products may be used alone as binder in coatingcompositions or, as illustrated above, they may be combined with othercoating resins such as the alkyd-type resins.

The products of this invention may also be used to impregnate cellulosicfilling materials for the preparation of laminated and molded productsfor which purpose the water-soluble condensates are preferred. They maybe combined with other nitrogen resins such as those based on urea,melamine, and other mono-(aminotriazines); and joint condensates withsuch resin-forming nitrogen compounds are contemplated. In this way themost desirable properties of a plurality of resins may be combined intoone product.

We claim:

1. A composition of matter comprising a condensation product offormaldehyde and a bis- (aminotriazine) oi the formula wherein R is analkyl group of one to eight carbon atoms and contains a hydrogen atom onthe carbon atom adjacent to the nitrogen atom, R1 is selecied from thegroup consisting of hydrogen and methyl, and R2 is an alkyl group of oneto eight carbon atoms.

2. A composition of matter comprising a condensation product offormaldehyde and a bis- (aminotriazine) of the formula no/ \N/ NHa 3. Acomposition of matter comprising the reaction product of six to ten molsof formaldehyde and one mol of a bis-(aminotriazine) of the formula RI RN t c I N=C 10 mols of formaldehyde and one mol of a bis-(aminotriazine) of the formula HIN/ N NHi wherein R is an alkyl group ofone to eight carbon atoms and contains a hydrogen atom on the carbonatom adjacent to the nitrogen atom, R1 is selected from the groupconsisting of hydrogen and methyl, and R2 is an alkyl group of one toeight carbon atoms, said reaction product being obtained by carrying outthe said reaction in butanol.

6. A composition of matter comprising the alcoholmodified reactionproduct of six to ten mols of formaldehyde and one mol of abis-(aminotriazine) of the formula said reaction product being obtainedby carrying out the said reaction in an alcoholic solvent.

'7. A composition of matter comprising the butanol-modifiecl reactionproduct of six to ten mols of formaldehyde and one mol of ahisaminotriazine) oi' the formula H:N/ \N/ \NH:

said reaction product being obtained by canying out the said reaction inbutanol.

8. A composition of matter comprising the alcohol-modiiied reactionproduct of six to ten 11 12 mols of formaldehyde and one moi of :1bissaid reaction product being obtained by carry- (aminotriazine) of theformula ing out the said reaction in an alcoholic solvent. NH, 11. Acomposition of matter comprising the butanoi-modified reaction productof six to ten CH N mols of formaldehyde and one moi of a.bis-(aminotriazine) oi the formula :Hn N=C /NH:

g cm /N-C\ l0 -c.m-N c /N said reaction product being obtained bycarrying out the said reaction in an alcoholic solvent. N N

9. A composition of matter comprising the bu- I tanoi-modified reactionproduct 01' six to ten mols 15 H of formaldehyde and one mol of abis-(aminotriazine) or the formula said reaction product being obtainedby carryins out the said reaction in butanol. I 50 CHr-N- G N PETER L.D! BENNEVILLE.

.i VINCENT CARR MEUNIER. N/ \N \NH:

References Cited in the tile of this patent mN \N/ NH, UNITED STATESPATENTS said reaction product being obtained by carry- Number Name D ming out the said reaction in buts-n01. 2,524,727 Dudley Oct. 3, 1950 10.A composition of matter comprising the ala0 cohol-modifled reactionproduct of six to ten mols of formaldehyde and one moi 01' abis-(aminotri- FOREIGN PATENTS azine) DI the formula Country Date608,186 Great Britain Sept. 10, 1948 CH: //N-G a5 nC|H:N( J-C :N

m N=O\ 3: 4; NH,

Certificate of Correction Patent No. 2,653,143 September 22, 1953 PETERL. DE BENNEVILLE ET AL.

Itis hereby certified that error appears in the printed specification ofthe above numbered patent requiring correction as follows:

Column 2, line 27, for dicyanodiamine read dz'cyanodz'amide; column 9,lines to 63, claim 3, for that portion of the formula reading and thatthe said Letters Patent should be read as corrected above, so that thesame may conform to the record of the case in the Patent Oifice. Signedand sealed this 10th day of November, A. D. 1953.

ARTHUR W. CROCKER,

Assistant Commissioner of Patents.

11 12 mols of formaldehyde and one moi of :1 bissaid reaction productbeing obtained by carry- (aminotriazine) of the formula ing out the saidreaction in an alcoholic solvent. NH, 11. A composition of mattercomprising the butanoi-modified reaction product of six to ten CH N molsof formaldehyde and one moi of a. bis-(aminotriazine) oi the formula :HnN=C /NH:

g cm /N-C\ l0 -c.m-N c /N said reaction product being obtained bycarrying out the said reaction in an alcoholic solvent. N N

9. A composition of matter comprising the bu- I tanoi-modified reactionproduct 01' six to ten mols 15 H of formaldehyde and one mol of abis-(aminotriazine) or the formula said reaction product being obtainedby carryins out the said reaction in butanol. I 50 CHr-N- G N PETER L.D! BENNEVILLE.

.i VINCENT CARR MEUNIER. N/ \N \NH:

References Cited in the tile of this patent mN \N/ NH, UNITED STATESPATENTS said reaction product being obtained by carry- Number Name D ming out the said reaction in buts-n01. 2,524,727 Dudley Oct. 3, 1950 10.A composition of matter comprising the ala0 cohol-modifled reactionproduct of six to ten mols of formaldehyde and one moi 01' abis-(aminotri- FOREIGN PATENTS azine) DI the formula Country Date608,186 Great Britain Sept. 10, 1948 CH: //N-G a5 nC|H:N( J-C :N

m N=O\ 3: 4; NH,

Certificate of Correction Patent No. 2,653,143 September 22, 1953 PETERL. DE BENNEVILLE ET AL.

Itis hereby certified that error appears in the printed specification ofthe above numbered patent requiring correction as follows:

Column 2, line 27, for dicyanodiamine read dz'cyanodz'amide; column 9,lines to 63, claim 3, for that portion of the formula reading and thatthe said Letters Patent should be read as corrected above, so that thesame may conform to the record of the case in the Patent Oifice. Signedand sealed this 10th day of November, A. D. 1953.

ARTHUR W. CROCKER,

Assistant Commissioner of Patents.

1. A COMPOSITION OF MATTER COMPRISING A CONDENSATION PRODUCT OFFORMALDEHYDE AND A BIS(AMINOTRIAZINE) OF THE FORMULA